Zeolite is a general name of minerals in aluminum silicic acid hydride of alkali and alkaline earth metal and classified to several kinds according to 3-dimensional pore structure, shape and size. In the basic structure of zeolite, cation intervenes the substitution of Al ion for Si ion to compensate charge loss and water molecules occupy extra space remained. Zeolite discharges cation or water molecule to accept other molecules into a pore if heated at 200-300° C. for some time period. By this process, it may retain the size selectivity and the shape selectivity of minute particles. Thus, zeolite is often used for a molecular sieve.
Besides, zeotype molecular sieve substituting total or partial Si and Al's of zeolite by other elements is applied industrially. For example, zeolite-like material displacing cations by metal ions is useful for a cracking catalyst of crude oil in a petrochemical industry. Zeolite and its similar material can be a host carrier for desiccant of dehydration, adsorbent, gas purifier, additive of detergent, ion exchanger, soil reformer, sensor and the like.
Traditionally in researches of zeolite and zeolite-like material, molecular sieve particles are attempted to adhere on the surface of carrier efficiently, since zeolite and its similar material exist in a minute powder.
Precisely, the method for attaching zeolite particles by physical attraction between the surfaces of zeolite and substrate, after soaking substrate in a suspension comprising zeolite crystal, is disclosed for the simplest process [L. C. Boudreau, J. A. Kuck, M. Tsapatsis, and J. Membr. Sci. 1999, 152, 41-59]. In this procedure, zeolite particles can hardly prepare a homogeneous mono-layer, because the speed for bringing out zeolite from suspension should be adjusted to control the degree of dispersion in zeolite. Further, zeolite tends to dissociate easily from a substrate because zeolite is just physically adsorbed onto a substrate.
In addition, the method for applying a compound having methyldimethoxysiryl group (Me(MeO)2Si—) at both ends as a spacer connecting substrate and zeolite, which comprises steps as follows: (a) combining a substrate and one methyldimethoxysiryl group in a compound having methyldimethoxysiryl groups at both ends by covalent bond; (b) mixing zeolite; and (c) inducing a covalent bond between the other methyldimethoxysiryl group and zeolite, is demonstrated [Z. Li, C. Lai, T. E. Mallouk, Inorg. Chem, 1989, 28, 178-182]. Unfortunately, zeolite cannot be controlled in the direction of particles, even if it is attached strongly, compared with other method for simply immersing zeolite in a suspension and rather, methyldimethoxysiryl groups at both ends of spacer may interfere with combining between a substrate and zeolite, since reacting with a substrate.
Besides, the method for attaching substrate and zeolite by using multi-step ionic bond, comprising steps (a) treating covalent-bonded aminopropyl group on the surface of substrate with chloric acid to confer positive charges on the surface by ammonium ions; and (b) treating sodium polystyrenesulfonic acid polymer on the surface of substrate to coat with negative-charged polymer, is described [L. C. Boudreau, J. A. Kuck, M. Tsapatsis, J. Membr. Sci. 1999, 152, 41-59]. This procedure is performed alternatively to form a thin membrane of zeolite by ionic bonding. Problematically, it is complicated to proceed more than 6 steps, cannot distribute zeolites exactly in an extent aspect, even if distributes uniformly and reduces the degree of coverage.
Furthermore, the method for synthesizing zeolite layer on the surface of substrate directly by enlarging the nucleus of zeolite particle on the surface, are suggested [J. C. Jansen, D. Kashchiev, A. Erdem-Senatalar, Stud, Surf. Catal. 1994, 85, 215-250]. Disadvantageously, substrate should not change the quality under a synthetic condition of zeolite and zeolite mono-layer cannot be controlled in the thickness, depending upon requirements.
Recently, zeolite and zeolite-like material are tried in various researches to be exploited for a new high-technological material since they can be manufactured to a nano-sized, small particle [G. A. Ozin, A. Kuperman, A. Stein, and Angew. Chem. Int. Ed. Engl. Adv. Mater. 28, 359 (1989)]. Especially, a use of host for 3-dimensional memory material [G. A. Ozin, A. Stein, G. D. Stucky, J. P. Godber, J. Inclusion Phenom. 6, 379 (1990)], apparatus for condensing light energy [M. Borja, P. K. Dutta, Nature 362, 43 (1993); M. Sykora, J. R. Kincaid, Nature 387, 162 (1997); Y. Kim et al., J. Phys. Chem. 101, 2491 (1997)], electrode supporting material [D. R. Rolison, C. A. Bessel, Acc. Chem. Res. 33, 737 (2000)], semi-conductor quantum dot and quantum wire [N. Hermon et al., J. Am. Chem. Soc. 111, 530 (1989)], molecular circuit [T. Bein, P. Enzel, Angew. Chem. Int. Ed. Engl. 12, 1737 (1989)], light sensor [G. Grubert, M. Stockenhuber, O. P. Tkachenko, M. Wark, Chem. Mater. 14, 2458 (2002)], luminescent body [G. Calzaferri et al., J. Mater. Chem. 12, 1 (2002)], nonlinear optical substance [S. D. Cox, T. E. Gier, G. D. Stucky, J. Bierlein, J. Am. Chem. Soc. 110, 2986 (1988)], raser luminescent element [U. Vietze et al., Phys. Rev. Lett. 81, 4628 (1998)] is actively investigated.
In order to settle disadvantages in the conventional methods for covering described above, the present inventors are tried to effectively utilize zeolite and its similar material recognized as a new high-technological material and developed a process for assembling 2-dimensional or 3-dimensional condensed structure (zeolite super-crystal) by distributing zeolite particles in a nano or micrometer size to a fixed direction [A. Kulak, Y.-J. Lee, Y. S. Park, K. B. Yoon, Angew. Chem. Int. Ed. 39, 950 (2000); S. Y. Choi Y. J. Lee, Y. S. Park, K. Ha, K. B. Yoon, J. Am. Chem. Soc. 122, 5201 (2000); A. Kulak, Y. S. Park, Y. J. Lee, Y. S. Chun, K. Ha, K. B. Yoon, J. Am. Chem. Soc. 122, 9308 (2000); G. S. Lee, Y. J. Lee, K. Ha, K. B. Yoon, Tetrahedron 56, 6965 (2000); K. Ha, Y. J. Lee, H. J. Lee, K. B. Yoon, Adv. Mater. 12, 1114 (2000); K. Ha, Y. J. Lee, D.-Y. Jung, J. H. Lee, K. B. Yoon, Adv. Mater. 12, 1614 (2000); G. S. Lee, Y.-J. Lee, K. B. Yoon, J. Am. Chem. Soc. 123, 9769 (2001); K. Ha, Y. J. Lee, Y. S. Chun, Y. S. Park, G. S. Lee, K. B. Yoon, Adv. Mater. 13, 594 (2001); G. S. Lee, Y. J. Lee, K. Ha, K. B. Yoon, Adv. Mater. 13, 1491 (2001); Y. S. Chun, K. Ha, Y. J. Lee, J. S. Lee, H. S. Kim, Y. S. Park, K. B. Yoon, Chem. Comm. 17, 1846 (2002); J. S. Park, G. S. Lee, Y. J. Lee, Y. S. Park, K. B. Yoon, J. Am. Chem. Soc. 124, 13366 (2002); J. S. Park, Y. J. Lee, K. B. Yoon, J. Am. Chem. Soc. 126, 1934 (2004); K. Ha, J. S. Park, K. S. Oh, Y. S. Zhou, Y. S. Chun, Y. J. Lee, K. B. Yoon, Micropor. Mesopor. Mater. (2004)]. In practice, the complex combining zeolite molecular sieve or its derivative onto substrate in a mono-layer or multi-layer and the method for preparation thereof are registered [Korean Pat No. 335966; PCT/KR00/01002].
In the above-mentioned patent, (1) the process for forming substrate-molecular sieve layer complex, which comprises steps (a) combining a substrate and a coupling compound (intermediate 1) by covalent bond; (b) combining molecular sieve particle and coupling compound (intermediate 2); and then, (c) combining intermediate 1 and intermediate 2 by using functional groups at the termini of 2 coupling compounds by covalent, ionic or coordinate bond; (2) the process for forming substrate-molecular sieve layer complex, which comprises steps (a) combining substrate or molecular sieve particle and one end of coupling compound by covalent bond; and (b) combining substrate or molecular sieve particle and the other end of coupling compound directly by covalent bond; (3) the process for forming substrate-molecular sieve layer complex by inserting a intermediate coupling compound between intermediate 1 and intermediate 2 to adjust the distance between a substrate and a molecular sieve particle; (4) the process for forming substrate-molecular sieve layer complex by performing the process (1)-(3) repeatedly; and the like are disclosed, which contributes to apply substrate-molecular sieve layer complex for new high-technological material. Unfortunately, this procedure is low in energy-efficiency and adhesion velocity, reduces compactness between zeolite particles and is low in bond strength between zeolite and substrate, because it adopts a simple reflux process to combine substrate and coupling compound, molecular sieve particle and coupling compound, coupling compound and coupling compound, and coupling compound and intermediate coupling compound. Moreover, it is difficult to prepare products in a large scale due to problematic simple reflux.